Equilibrium Reactions In any reaction the reactants react to give products.

. In the generic reaction below, a moles of reactant A react with b moles of reactant B to give c moles of product C and d moles of product D. aA + bB cC + dD

The reaction will stop when either A or B is completely used up. A reaction of this type is said to go to completion. Most reactions are not of this type. Most reactions are equilibrium reactions. In an equilibrium reaction the reactants react to give products, but the products, in turn, react with each other to give the reactants. We indicate this by using forward and reverse reaction arrows aA + bB cC + dD The rate of the forward reaction is rateforward = kforward[A]a [B]b, where kforward is the rate constant of the forward reaction. The larger kforward the faster a molecule of A will react with one of B. The rate of the reverse reaction is ratereverse = kreverse[C] c [D] d, where kreverse is the rate constant of the reverse reaction. The larger kreverse the faster a molecule of C will react with one of D. At equilibrium, rateforward = ratereverse and the concentrations of A, B, C, and D do not change with time even though reaction is taking place. At

equilibrium, since rateforward = ratereverse, kforward[A]a [B]b = kreverse[C] c [D] d,

kforward [C]c [D]d kforward or . The ratio is known = a b k kreverse [A] [B] reverse
as the equilibrium constant, Keq, for the reaction. So,

Keq =

[C]c [D]d [A]a [B]b

Acids & Bases Bronsted/Lowry: acid: substance which gives up a proton base: substance which accepts a proton HA acidgives H+ to B to form A+ B baseaccepts H+ from HA to form HB+ baseaccepts H+ from HB+ to form HA conjugate base of HA conjugate acid of Aconjugate base of HB+ acidgives H+ to A- to form B conjugate acid of B A+ HB+

Acids and bases may be charged or uncharged --Acid H2S HS

-

Base + + H2O OH
-

Acid H3O + H2O + +

Base SHS-2

HCl + H2N(CH2) 4NH3+

H3N(CH2)4NH3+2 + Cl-

Typically, acids are neutral or positive, bases are neutral or negative.

Acid and Base Strength: At equilibrium the weaker acid and base are favored. SA=stronger acid WA=weaker acid HCl + H2O SB SA O H3C C OH + H2O WB WA O H3C C OH + OH SB SA H3C H3C SB=stronger base WB=weaker base Cl + H3O WA WB O C O + H3O SA SB O C O + H2O WA WB

Therefore, acid strength: HCl > H3O+ > H3CCOOH > H2O base strength: OH > H3 CCOO > H2O > Cl Note that the stronger an acid is, the weaker its conjugate base is. Does this make sense to you? [It should!] Quantative measure of Bronsted-Lowry acidity HA + H2O A + H3O

Keq =

[A] [H3O] [HA] [H2O]

but in dilute solutions [H2O] ~ 55.5M i.e. there are ~55.5 moles of water in a liter of dilute aqueous solution, so...

Keq =

[A] [H3O] [HA] (55.5) [A] [H3O] [HA]

or

Keq (55.5) =

= Ka

pKa = -logKa The smaller (or the more negative) the pKa, the larger the Ka, and the stronger the acid.

Lewis definitions of acid and base Acid: an electron pair acceptor. Base: an electron pair donor. Lowry-Bronsted acids and bases are a subset of Lewis acids and bases; every L-B acid is a Lewis acid, every L-B base is a Lewis base. H3O+ acid by L-B and Lewis :NH3 base by L-B and Lewis BF3 acid by Lewis, but not by L-B (no proton to donate) H3N: + BF3 H3N+BF3

Acid-Base Chemistry in Action: Lab Experiment Synthesis of Dibenzalacetone Overall reaction O O OH-

2 C6H5 C H + H3C C CH3 acetone benzaldehyde O

C6H5 CH CH C CH CH C6H5 + 2 H2O dibenzalacetone [Sometimes when we write the equations for reactions in organic chemistry we write the formulas of one or more of the reactants above or below the reaction arrow. In this case the hydroxide ion (from sodium or potassium hydroxide) is a catalyst in the reaction and, so, is not consumed. Color is used here to show how fragments within the dibenzalacetone molecule derive from the two components that react.] The Reaction Mechanism The equation above tells us what happens, overall, in the reaction. The equation tells us that two molecules of benzaldehyde react with one molecule of acetone, in the presence of hydroxide ion, to give one molecule of dibenzalacetone and two molecules of water; it does not tell us how this happens. The reaction mechanism tells us how the reactants are converted into products. To use a sports analogy, knowing the overall reaction

is like knowing that the Dodgers played the Mets last night and the Mets won, 3 to 2. Knowing the details of the reaction mechanism is like knowing the play-byplay of the game. The reaction mechanism for this reaction involves a lot of acid-base chemistry as do many, if not most, reaction mechanisms. The Mechanism In the first step, acetone functions as a Bronsted-Lowry acid and hydroxide as a base. Note that the equilibrium for this step is not favorable: water (pKa = 15.7) is a stronger acid than acetone (pKa ~ 20). Nevertheless, the overall reaction is successful because the equilibrium for the final step in the mechanism is favorable. Note the use of curved arrows in the mechanism. The curves arrows are bookkeeping devices they track the movements of electrons. O H O H H3C C C H H + OH H3C C C + H2O H
There is another resonance form for this anion. Can you draw it?

The next step involves the anion formed in the first step acting as a Lewis base in its attack on the partially positively charged C=O carbon of benzaldehyde to form a covalent bond that joins these two moieties together.

O H3C C

H C H + H

O C C6H5 O H3C C H C H O C H C6H5

The next step is simply a B-L acid-base reaction with water functioning as the acid. O H3C C H C H O C H H3C C6H5 + H2O O C H C H O C H H C6H5 + OH

The next step involves what is known as an elimination reaction. In an elimination reaction a couple of moieties (atoms or groups of atoms) are removed from a molecule generating the products. In this case the elimination reaction involves a B-L acid-base reaction with hydroxide as the base.

OH O H3C C H C H O C H H3C H C6H5 O C C H C H C6H5 H2O +

At this point we are halfway to the final product. Looking back, we started with acetone and converted the -CH3 group on the right side into a CH=CH-C6H5 group. Using the same series of steps, it is now possible to convert the remaining -CH3 into a CH=CH-C6H5 group to produce the final product.

Do it!